Azeotropic compositions of hydrogen fluoride and z-3,3,3-trifluoro-1-chloropropene

ABSTRACT

A process for producing a main (hydro)halocarbon compound, including the formation of a mixture of compounds including hydrogen fluoride, Z-3,3,3-trifluoro-1-chloropropene and one or more other (hydro)halocarbon compounds, distillation of this mixture making it possible to collect, firstly, an azeotropic composition, and, secondly, at least one of the compounds of the mixture. The (hydro) halocarbon compounds are preferably selected among tetrachlorofluoropropanes, trichlorodifluoropropanes, dichlorotrifluoropropanes, chlorotetrafluoropropanes, pentafluoropropanes, dichlorodifluoropropenes, chlorotrifluoropropenes and tetrafluoropropenes.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application is a divisional of U.S. application Ser. No.15/104,836, filed on Jun. 15, 2016, which is a U.S. national stage ofInternational Application No. PCT/FR2014/053228, filed on Dec. 9, 2014,which claims the benefit of French Application No. 13.62982, filed onDec. 19, 2013. The entire contents of each of U.S. application Ser. No.15/104,836, International Application No. PCT/FR2014/053228, and FrenchApplication No. 13.62982 are hereby incorporated herein by reference intheir entirety.

TECHNICAL FIELD

The present invention relates to azeotropic or quasi-azeotropiccompositions based on hydrogen fluoride andZ-3,3,3-trifluoro-1-chloropropene.

TECHNICAL BACKGROUND

3,3,3-Trifluoro-1-chloropropene, also known as1-chloro-3,3,3-trifluoropropene (HCFO-1233zd), exists in the form of twoisomers: the cis isomer, namely Z-3,3,3-trifluoro-1-chloropropene(HCFO-1233zdZ), and the trans isomer, namelyE-3,3,3-trifluoro-1-chloropropene (HCFO-1233zdE). They have differentboiling points: 18.5° C. for the trans compound and 39.5° C. for the ciscompound, respectively.

Fluids based on E-3,3,3-trifluoro-1-chloropropene (HCFO-1233zdE) havefound numerous applications in varied industrial fields, especially asheat-transfer fluids, propellants, foaming agents, swelling agents,gaseous dielectrics, polymerization media or monomers, support fluids,abrasives, drying agents and fluids for power production units.

The manufacture of HCFO-1233zdE is accompanied by a multitude ofby-products, having a boiling point close to HCFO-1233zdE. This leads toquite complex and expensive purification steps. The difficultiesencountered during the purification of HCFO-1233zdE generally entail aconsequent loss of the desired product. Furthermore, the by-products mayform azeotropic compositions with HCFO-1233zdE, making separation bysimple distillation very difficult or even impossible.

U.S. Pat. No. 6,013,846 describes an azeotropic composition ofHCFO-1233zd and hydrogen fluoride (HF). The document does not mentionthe isomeric form of HCFO-1233zd.

U.S. Pat. No. 6,328,907 describes an azeotropic composition of1,1,1,3,3-pentafluoropropane (HFC-245fa) and HF.

U.S. Pat. No. 8,378,158 describes a quasi-azeotropic composition ofHCFO-1233zdZ and HF.

U.S. Pat. No. 7,423,188 describes an azeotropic composition ofE-1,3,3,3-tetrafluoropropene (HFO-1234zeE) and HF.

WO 2008/002500 describes an azeotropic composition ofZ-1,3,3,3-tetrafluoropropene (HFO-1234zeZ) and HF.

U.S. Pat. No. 7,183,448 describes an azeotropic composition of HFC-245faand HCFO-1233zd. It is pointed out in the document that the azeotrope isobtained with the trans isomer of HCFO-1233zd.

U.S. Pat. No. 8,075,797 describes a quasi-azeotropic composition of HF,HFC-245fa and HCFO-1233zd. It is pointed out in the document that thequasi-azeotrope is obtained with the—trans isomer of HCFO-1233zd.

There is still a need to provide other azeotropic compositions andespecially azeotropic compositions based on compounds that canparticipate in the manufacture of HCFO-1233zdE. However, in general,azeotropes are difficult to predict.

SUMMARY OF THE INVENTION

The invention relates firstly to an azeotropic or quasi-azeotropiccomposition comprising hydrogen fluoride,Z-3,3,3-trifluoro-1-chloropropene and one or more (hydro)halocarboncompounds comprising from 1 to 3 carbon atoms.

According to one embodiment, the (hydro)halocarbon compound(s) comprisethree carbon atoms, and are preferably chosen from propanes and propenesthat are partially or totally substituted with halogens.

According to one embodiment, the (hydro)halocarbon compound(s) arechosen from tetrachlorofluoropropanes, trichlorodifluoropropanes,dichlorotrifluoropropanes, chlorotetrafluoropropanes,pentafluoropropanes, trichlorofluoropropenes, dichlorodifluoropropenes,chlorotrifluoropropenes and tetrafluoropropenes.

According to one embodiment, the composition of the invention compriseshydrogen fluoride, Z-3,3,3-trifluoro-1-chloropropene,E-3,3,3-trifluoro-1-chloropropene and one or more other(hydro)halocarbon compounds comprising from 1 to 3 carbon atoms.

According to one embodiment, the composition of the invention compriseshydrogen fluoride, Z-3,3,3-trifluoro-1-chloropropene,E-1,3,3,3-tetrafluoropropene and one or more other (hydro)halocarboncompounds comprising from 1 to 3 carbon atoms.

According to one embodiment, the composition of the invention compriseshydrogen fluoride, Z-3,3,3-trifluoro-1-chloropropene,Z-1,3,3,3-tetrafluoropropene and one or more other (hydro)halocarboncompounds comprising from 1 to 3 carbon atoms.

According to one embodiment, the composition of the invention compriseshydrogen fluoride, Z-3,3,3-trifluoro-1-chloropropene,1,1,1,3,3-pentafluoropropane and one or more other (hydro)halocarboncompounds comprising from 1 to 3 carbon atoms.

According to one embodiment, the composition of the invention is aternary mixture, and is preferably a mixture of hydrogen fluoride,Z-3,3,3-trifluoro-1-chloropropene and E-3,3,3-trifluoro-1-chloropropene.

According to one embodiment, the composition of the invention is aquaternary mixture, and is preferably a mixture of:

-   -   hydrogen fluoride, Z-3,3,3-trifluoro-1-chloropropene,        E-3,3,3-trifluoro-1-chloropropene and        1,1,1,3,3-pentafluoropropane; or    -   hydrogen fluoride, Z-3,3,3-trifluoro-1-chloropropene,        E-1,3,3,3-tetrafluoropropene and 1,1,1,3,3-pentafluoropropane;        or    -   hydrogen fluoride, Z-3,3,3-trifluoro-1-chloropropene,        Z-1,3,3,3-tetrafluoropropene and 1,1,1,3,3-pentafluoropropane.

According to one embodiment, the composition of the invention is aquinternary mixture, and is preferably a mixture of:

-   -   hydrogen fluoride, Z-3,3,3-trifluoro-1-chloropropene,        E-3,3,3-trifluoro-1-chloropropene, Z 1,3,3,3-tetrafluoropropene        and 1,1,1,3,3-pentafluoropropane; or    -   hydrogen fluoride, Z-3,3,3-trifluoro-1-chloropropene,        E-3,3,3-trifluoro-1-chloropropene, E 1,3,3,3-tetrafluoropropene        and 1,1,1,3,3-pentafluoropropane; or    -   hydrogen fluoride, Z-3,3,3-trifluoro-1-chloropropene,        Z-1,3,3,3-tetrafluoropropene, E-1,3,3,3-tetrafluoropropene and        1,1,1,3,3-pentafluoropropane.

According to one embodiment, the composition of the invention is asenary mixture, and is preferably a mixture of:

-   -   hydrogen fluoride, Z-3,3,3-trifluoro-1-chloropropene,        E-3,3,3-trifluoro-1-chloropropene, Z-1,3,3,3-tetrafluoropropene,        E-1,3,3,3-tetrafluoropropene and 1,1,1,3,3-pentafluoropropane.

According to one embodiment, the composition according to the inventionis hetero-azeotropic or quasi-hetero-azeotropic.

According to one embodiment, the composition of the invention comprisesfrom 1% to 85% by weight, preferably from1% to 80% by weight, moreparticularly preferably from 5% to 80% by weight and most particularlypreferably from 5% to 75% by weight of hydrogen fluoride; and/or from15% to 99% by weight, preferably from 20% to 99% by weight, moreparticularly preferably from 20% to 95% by weight and most particularlypreferably from 25% to 95% by weight of (hydro)halocarbon compoundscomprising from 1 to 3 carbon atoms.

According to one embodiment, the composition of the invention has aboiling point of 0 to 40° C. for a pressure from 0.5 to 9 bar absolute.

The invention also relates to a process for producing a main(hydro)halocarbon compound, comprising:

-   -   the formation of a mixture of compounds comprising hydrogen        fluoride, Z-3,3,3-trifluoro-1-chloropropene and one or more        other (hydro)halocarbon compounds;    -   distillation of this mixture making it possible to collect,        firstly, an azeotropic composition of the invention, and,        secondly, at least one of the compounds of the mixture.

According to one embodiment, distillation makes it possible to collect,firstly, an azeotropic composition of the invention, and, secondly,hydrogen fluoride; or alternatively, firstly, an azeotropic compositionof the invention, and, secondly, E-3,3,3-trifluoro-1-chloropropene.

According to one embodiment, the process of the invention is a processfor producing 3,3,3-trifluoro-1-chloropropene, and preferablyE-3,3,3-trifluoro-1-chloropropene.

According to one embodiment, the mixture of compounds is obtained aftera fluorination step, comprising the reaction of a chloro compound withhydrogen fluoride.

According to one embodiment, the azeotropic composition collected isseparated, preferably by decantation, into two immiscible liquidfractions, namely a fraction rich in hydrogen fluoride and a fractionpoor in hydrogen fluoride, the fraction rich in hydrogen fluoridecontaining a higher proportion of hydrogen fluoride than the fractionpoor in hydrogen fluoride; and the fraction rich in hydrogen fluoridebeing, where appropriate, recycled into the fluorination step. Thefraction poor in hydrogen fluoride may undergo distillation to allow thecollection, firstly, of an azeotropic composition of the invention and,secondly, of E-3,3,3-trifluoro-1-chloropropene.

According to one embodiment, the starting chloro compound that reactswith hydrogen fluoride is 1,1,1,3,3-pentachloropropane or1,1,3,3-tetrachloropropene.

The present invention makes it possible to satisfy the need expressedabove. It more particularly provides azeotropic or quasi-azeotropiccompositions from compounds that can participate in the manufacture ofvarious (hydro)halocarbon compounds, and especially in the manufactureof HCFO-1233zdE.

Identification of these azeotropic or quasi-azeotropic compositions thusmakes it possible especially to improve the efficiency and performanceof processes for producing (hydro)halocarbon compounds, and especiallyfor producing HCFO-1233zdE.

In a preferred embodiment, these compositions are hetero-azeotropic,i.e. they are compositions whose condensed liquid forms two immisciblesolutions that may be readily separated, for example by decantation.This entails a considerable advantage for the envisaged purificationoperations.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 represents the vapor pressure (on the y-axis, in bar absolute) ofmixtures according to the invention in accordance with Example 1, forthe 25° C. isotherm. The mass fraction of HF in the composition is givenon the x-axis. Curves A, B and C correspond to various compositions of(hydro)halocarbon compounds (see Example 1).

FIG. 2 represents the vapor pressure (on the y-axis, in bar absolute) ofmixtures according to the invention in accordance with Example 2, forthe 25° C. isotherm. The mass fraction of HF in the composition is givenon the x-axis. Curves A, B, C and D correspond to various compositionsof (hydro)halocarbon compounds (see Example 2).

FIG. 3 represents the vapor pressure (on the y-axis, in bar absolute) ofmixtures according to the invention in accordance with Example 3, forthe 25° C. isotherm. The mass fraction of HF in the composition is givenon the x-axis. Curves A, B, C and D correspond to various compositionsof (hydro)halocarbon compounds (see Example 3).

FIG. 4 represents the vapor pressure (on the y-axis, in bar absolute) ofmixtures according to the invention in accordance with Example 4, forthe 25° C. isotherm. The mass fraction of HF in the composition is givenon the x-axis. Curves A, B, C and D correspond to various compositionsof (hydro)halocarbon compounds (see Example 4).

FIG. 5 represents the vapor pressure (on the y-axis, in bar absolute) ofmixtures according to the invention in accordance with Example 5, forthe 25° C. isotherm. The mass fraction of HF in the composition is givenon the x-axis. Curves A, B, C, D and E correspond to variouscompositions of (hydro)halocarbon compounds (see Example 5).

FIG. 6 represents the vapor pressure (on the y-axis, in bar absolute) ofmixtures according to the invention in accordance with Example 6, forthe 25° C. isotherm. The mass fraction of HF in the composition is givenon the x-axis. Curves A, B, C, D and E correspond to variouscompositions of (hydro)halocarbon compounds (see Example 6).

FIG. 7 represents the vapor pressure (on the y-axis, in bar absolute) ofmixtures according to the invention in accordance with Example 7, forthe 25° C. isotherm. The mass fraction of HF in the composition is givenon the x-axis. Curves A, B, C, D and E correspond to variouscompositions of (hydro)halocarbon compounds (see Example 7).

FIG. 8 represents the vapor pressure (on the y-axis, in bar absolute) ofmixtures according to the invention in accordance with Example 8, forthe 25° C. isotherm. The mass fraction of HF in the composition is givenon the x-axis. Curves A, B, C, D, E and F correspond to variouscompositions of (hydro)halocarbon compounds (see Example 8).

DESCRIPTION OF EMBODIMENTS OF THE INVENTION

The invention is now described in greater detail and in a nonlimitingmanner in the description that follows.

Unless otherwise mentioned, all proportions mentioned in the presentpatent application are mass proportions.

The invention provides azeotropic, quasi-azeotropic, hetero-azeotropicand quasi-hetero-azeotropic compositions.

A mixture is considered as azeotropic when the pressure at the dew pointis equal to that at the bubble formation point, which means that thecomposition of the vapor is equal to that of the condensed liquid.

A mixture is considered as quasi-azeotropic when the pressure at the dewpoint is substantially equal to that at the bubble formation point,which means that the vapor composition is substantially equal to that ofthe condensed liquid: for example, the pressure difference between thepressure at the dew point and the pressure at the bubble formation pointis less than or equal to 5% on the basis of the pressure at the bubbleformation point.

A hetero-azeotropic mixture is an azeotropic mixture whose condensedliquid forms two immiscible solutions that may be readily separated, forexample by decantation.

A quasi-hetero-azeotropic mixture is a quasi-azeotropic mixture whosecondensed liquid forms two immiscible solutions that may be readilyseparated, for example by decantation.

The compositions according to the invention comprise HF, HCFO-1233zdZand one or more (hydro)halocarbon compounds comprising from 1 to 3carbon atoms.

(Hydro)halocarbon compounds are compounds based on carbon, halogen andoptionally hydrogen atoms; advantageously, they are compounds based oncarbon, chlorine and/or fluorine and optionally hydrogen atoms. They areadvantageously alkanes or alkenes that are partially or totallysubstituted with halogen atoms, especially chlorine and/or fluorine.

According to a particular embodiment, the (hydro)halocarbon compoundsthat may be used in the context of the invention comprise 1 or 2 carbonatoms.

They may be chosen especially from:

-   -   chloromethane (HCC-40);    -   chloropentafluoroethane (HCFC-115);    -   chlorotetrafluoroethane (HFCF-124), namely        1-chloro-1,2,2,2-tetrafluoroethane and        1-chloro-1,1,2,2-tetrafluoroethane;    -   pentafluoroethane (HFC-125);    -   chlorotrifluoroethane, namely, in particular        1-chloro-1,2,2-trifluoroethane

(HCFC-133), 1-chloro-2,2,2-trifluoroethane (HCFC-133a) and1-chloro-1,1,2-trifluoroethane (HCFC-133b);

-   -   tetrafluoroethane, namely, in particular        1,1,2,2-tetrafluoroethane (HFC-134) and        1,1,1,2-tetrafluoroethane (HFC-134a);    -   chlorodifluoroethane, namely, in particular        1-chloro-2,2-difluoroethane (HCFC-142),        1-chloro-1,2-difluoroethane (HCFC-142a) and        1-chloro-1,1-difluoroethane (HCFC-142b);    -   trifluoroethane, namely, in particular 1,1,2-trifluoroethane        (HFC-143) and 1,1,1-trifluoroethane (HFC-143a);    -   difluoroethane, namely, in particular 1,1-difluoroethane        (HFC-152a) and 1,2-difluoroethane (HFC-152);    -   difluoroethylene, namely 1,2-difluoroethylene (HFO-1132) and        1,1-difluoroethylene (HFO-1132a); and    -   fluoroethylene (HFO-1141).

According to a particular embodiment, the (hydro)halocarbon compoundsthat may be used in the context of the invention comprise 3 carbonatoms.

They may be chosen especially from:

-   -   dichlorohexafluoropropane, namely, in particular        1,2-dichloro-1,1,2,3,3,3-hexafluoropropane (HCFC-216ba),        1,3-dichloro-1,1,2,2,3,3-hexafluoropropane (HCFC-216ca),        1,1-dichloro-1,2,2,3,3,3-hexafluoropropane (HCFC-216cb) and        2,2-dichloro-1,1,1,3,3,3-hexafluoropropane (HCFC-216aa);    -   chloroheptafluoropropane, namely, in particular        1-chloro-1,1,2,2,3,3,3-heptafluoropropane (HCFC-217ca) and        2-chloro-1,1,1,2,3,3,3-heptafluoropropane (HCFC-217ba);    -   octafluoropropane (HFC-218);    -   dichloropentafluoropropane, namely, in particular        2,2-dichloro-1,1,1,3,3-pentafluoropropane (HCFC-225aa),        2,3-dichloro-1,1,1,2,3-pentafluoropropane (HCFC-225ba),        1,2-dichloro-1,1,2,3,3-pentafluoropropane (HCFC-225bb),        3,3-dichloro-1,1,1,2,2-pentafluoropropane (HCFC-225ca),        1,3-dichloro-1,1,2,2,3-pentafluoropropane (HCFC-225cb),        1,1-dichloro-1,2,2,3,3-pentafluoropropane (HCFC-225cc),        1,2-dichloro-1,1,3,3,3-pentafluoropropane (HCFC-225da),        1,3-dichloro-1,1,2,3,3-pentafluoropropane (HCFC-225ea) and        1,1-dichloro-1,2,3,3,3-pentafluoropropane (HCFC-225eb);    -   chlorohexafluoropropane, namely, in particular        2-chloro-1,1,1,2,3,3-hexafluoropropane (HCFC-226ba),        3-chloro-1,1,1,2,2,3-hexafluoropropane (HCFC-226ca),        1-chloro-1,1,2,2,3,3-hexafluoropropane (HCFC-226cb),        2-chloro-1,1,1,3,3,3-hexafluoropropane (HCFC-226da) and        1-chloro-1,1,2,3,3,3-hexafluoropropane (HCFC-226ea);    -   heptafluoropropane, namely, in particular        1,1,2,2,3,3,3-heptafluoropropane (HFC-227ca) and        1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea);    -   dichlorotetrafluoropropane, namely, in particular        2,2-dichloro-1,1,3,3-tetrafluoropropane (HCFC-234aa),        2,2-dichloro-1,1,1,3-tetrafluoropropane (HCFC-234ab),        1,2-dichloro-1,2,3,3-tetrafluoropropane (HCFC-234ba),        2,3-dichloro-1,1,1,2-tetrafluoropropane (HCFC-234bb),        1,2-dichloro-1,1,2,3-tetrafluoropropane (HCFC-234bc),        1,3-dichloro-1,2,2,3-tetrafluoropropane (HCFC-234ca),        1,1-dichloro-2,2,3,3-tetrafluoropropane (HCFC-234cb),        1,3-dichloro-1,1,2,2-tetrafluoropropane (HCFC-234cc),        1,1-dichloro-1,2,2,3-tetrafluoropropane (HCFC-234cd),        2,3-dichloro-1,1,1,3-tetrafluoropropane (HCFC-234da),        1,3-dichloro-1,1,3,3-tetrafluoropropane (HCFC-234fa),        1,1-dichloro-1,3,3,3-tetrafluoropropane (HCFC-234fb),        1,1-dichloro-2,3,3,3-tetrafluoropropane (HCFC-234ea),        1,3-dichloro-1,1,2,3-tetrafluoropropane (HCFC-234eb)        1,1-dichloro-1,2,3,3-tetrafluoropropane (HCFC-234ec) and 1,2        dichloro-1,1,3,3-tetrafluoropentane (HCFC-234db);    -   chloropentafluoropropane, namely, in particular        1-chloro-1,2,2,3,3-pentafluoropropane (HCFC-235ca),        3-chloro-1,1,1,2,3-pentafluoropropane (HCFC-235ea),        1-chloro-1,1,2,2,3-pentafluoropropane (HCFC-235cc),        2-chloro-1,1,1,3,3-pentafluoropropane (HCFC-235da),        1-chloro-1,1,3,3,3-pentafluoropropane (HCFC-235fa),        1-chloro-1,1,2,3,3-pentafluoropropane (HCFC-235eb),        3-chloro-1,1,1,2,2-pentafluoropropane (HCFC-235cb),        2-chloro-1,1,2,3,3-pentafluoropropane (HCFC-235ba) and        2-chloro-1,1,1,2,3-pentafluoropropane (HCFC-235bb);    -   hexafluoropropane, namely, in particular        1,1,1,2,2,3-hexafluoropropane (HFC-236cb),        1,1,1,2,3,3-hexafluoropropane (HFC-236ea),        1,1,1,3,3,3-hexafluoropropane (HFC-236fa) and        1,1,2,2,3,3-hexafluoropropane (HFC-236ca);    -   tetrachlorofluoropropane, namely, in particular        1,1,3,3-tetrachloro-1-fluoropropane (HCFC-241fa),        1,1,1,3-tetrachloro-3-fluoropropane (HCFC-241fb),        1,1,3,3-tetrachloro-2-fluoropropane (HCFC-241ea),        1,1,1,3-tetrachloro-2-fluoropropane (HCFC-241eb),        1,1,2,3-tetrachloro-3-fluoropropane (HCFC-241da),        1,1,2,3-tetrachloro-1-fluoropropane (HCFC-241db),        1,1,1,2-tetrachloro-3-fluoropropane (HCFC-241dc),        1,1,2,3-tetrachloro-2-fluoropropane (HCFC-241ba),        1,1,1,2-tetrachloro-2-fluoropropane (HCFC-241bb),        1,2,2,3-tetrachloro-1-fluoropropane (HCFC-241aa),        1,1,2,2-tetrachloro-3-fluoropropane (HCFC-241ab) and        1,1,2,2-tetrachloro-1-fluoropropane (HCFC-241ac);    -   trichlorodifluoropropane, namely, in particular        1,3,3-trichloro-1,1-difluoropropane (HCFC-242fa),        1,1,3-trichloro-1,3-difluoropropane (HCFC-242fb),        1,1,1,-trichloro-3,3-difluoropropane (HCFC-242fc),        1,1,3-trichloro-2,3-difluoropropane (HCFC-242ea),        1,1,3-trichloro-1,2-difluoropropane (HCFC-242eb),        1,1,1-trichloro-2,3-difluoropropane (HCFC-242ec),        1,2,3-trichloro-1,3-difluoropropane (HCFC-242da),        1,1,2-trichloro-3,3-difluoropropane (HCFC-242db),        1,2,3-trichloro-1,1-difluoropropane (HCFC-242dc),        1,1,2-dichloro-1,3-difluoropropane (HCFC-242dd),        1,1,3-trichloro-2,2-difluoropropane (HCFC-242ca),        1,1,1-trichloro-2,2-difluoropropane (HCFC-242cb),        1,2,3-trichloro-1,2-difluoropropane (HCFC-242ba),        1,1,2-trichloro-2,3-difluoropropane (HCFC-242bb),        1,1,2-trichloro-1,2-difluoropropane (HCFC-242bc),        2,2,3-trichloro-1,1-difluoropropane (HCFC-242aa),        1,2,2-trichloro-1,3-difluoropropane (HCFC-242ab) and        1,2,2-trichloro-1,1-difluoropropane (HCFC-242ac);    -   dichlorotrifluoropropane, namely, in particular        1,1-dichloro-3,3,3-trifluoropropane (HCFC-243fa),        1,3-dichloro-1,1,3-trifluoropropane (HCFC-243fb),        1,1-dichloro-1,3,3-trifluoropropane (HCFC-243fc),        1,3-dichloro-1,2,3-trifluoropropane (HCFC-243ea),        1,1-dichloro-2,3,3-trifluoropropane (HCFC-243eb),        1,3-dichloro-1,1,2-trifluoropropane (HCFC-243ec),        1,1-dichloro-1,2,3-trifluoropropane (HCFC-243ed),        1,2-dichloro-1,3,3-trifluoropropane (HCFC-243da),        2,3-dichloro-1,1,1-trifluoropropane (HCFC-243db),        1,2-dichloro-1,1,3-trifluoropropane (HCFC-243dc),        1,3-dichloro-1,2,2-trifluoropropane (HCFC-243ca),        1,1-dichloro-2,2,3-trifluoropropane (HCFC-243cb),        1,1-dichloro-1,2,2-trifluoropropane (HCFC-243cc),        2,3-dichloro-1,1,2-trifluoropropane (HCFC-243ba),        1,2-dichloro-1,2,3-trifluoropropane (HCFC-243bb),        1,2-dichloro-1,1,2-trifluoropropane (HCFC-243bc),        2,2-dichloro-1,1,3-trifluoropropane (HCFC-243aa) and        2,2-dichloro-3,3,3-trifluoropropane (HCFC-243ab);    -   chlorotetrafluoropropane, namely, in particular        2-chloro-1,2,3,3-tetrafluoropropane (HCFC-244ba),        2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb),        3-chloro-1,1,2,2-tetrafluoropropane (HCFC-244ca),        1-chloro-1,2,2,3-tetrafluoropropane (HCFC-244cb),        1-chloro-1,1,2,2-tetrafluoropropane (HCFC-244cc),        2-chloro-1,1,3,3-tetrafluoropropane (HCFC-244da),        2-chloro-1,1,1,3-tetrafluoropropane (HCFC-244db),        3-chloro-1,1,2,3-tetrafluoropropane (HCFC-244ea),        3-chloro-1,1,1,2-tetrafluoropropane (HCFC-244eb),        1-chloro-1,1,2,3-tetrafluoropropane (HCFC-244ec),        3-chloro-1,1,1,3-tetrafluoropropane (HCFC-244fa) and        1-chloro-1,1,3,3-tetrafluoropropane (HCFC-244fb);    -   pentafluoropropane, namely, in particular        1,1,2,2,3-pentafluoropropane (HFC-245ca),        1,1,2,3,3-pentafluoropropane (HFC-245ea),        1,1,1,2,3-pentafluoropropane (HFC-245eb),        1,1,1,2,2-pentafluoropropane (HFC-245cb) and        1,1,1,3,3-pentafluoropropane (HFC-245fa);    -   chlorotrifluoropropane, namely, in particular        2-chloro-1,2,3-trifluoropropane (HCFC-253ba),        2-chloro-1,1,2-trifluoropropane (HCFC-253bb),        1-chloro-2,2,3-trifluoropropane (HCFC-253ca),        1-chloro-1,2,2-trifluoropropane (HCFC-253cb),        3-chloro-1,1,2-trifluoropropane (HCFC-253ea),        1-chloro-1,2,3-trifluoropropane (HCFC-253eb),        1-chloro-1,1,2-trifluoropropane (HCFC-253ec),        1-chloro-1,3,3-trifluoropropane (HCFC-253fa),        3-chloro-1,1,1-trifluoropropane (HCFC-253fb),        1-chloro-1,1,3-trifluoropropane (HCFC-253fc),        2-chloro-1,1,3-trifluoropropane (HCFC-253da) and        2-chloro-1,1,1-trifluoropropane (HCFC-253db);    -   tetrafluoropropane, namely, in particular        1,1,2,2-tetrafluoropropane (HFC-254cb),        1,1,1,3-tetrafluoropropane (HFC-254fb),        1,1,2,3-tetrafluoropropane (HFC-254ea),        1,1,1,2-tetrafluoropropane (HFC-254eb),        1,2,2,3-tetrafluoropropane (HFC-254ca) and        1,1,3,3-tetrafluoropropane (HFC-254fa);    -   chlorodifluoropropane, namely, in particular        1-chloro-2,2-difluoropropane (HCFC-262ca),        3-chloro-1,1-difluoropropane (HCFC-262fa),        1-chloro-1,3-difluoropropane (HCFC-262fb),        1-chloro-1,1-difluoropropane (HCFC-262fc),        1-chloro-2,3-difluoropropane (HCFC-262ea),        1-chloro-1,2-difluoropropane (HCFC-262eb),        2-chloro-1,3-difluoropropane (HCFC-262da),        2-chloro-1,1-difluoropropane (HCFC-262db) and        2-chloro-1,2-difluoropropane (HCFC-262ba);    -   trifluoropropane (HFC-263), namely, in particular        1,1,1-trifluoropropane (HFC-263fb), 1,1,3-trifluoropropane        (HFC-263fa), 1,2,3-trifluoropropane (HFC-263ea),        1,1,2-trifluoropropane (HFC-263eb) and 1,2,2-trifluoropropane        (HFC-263ca);    -   dichlorotetrafluoropropene (HCFO-1214), namely, in particular        1,2-dichloro-1,3,3,3-tetrafluoropropene (HCFO-1214xb),        1,1-dichloro-2,3,3,3-tetrafluoropropene (HCFO-1214ya),        1,3-dichloro-1,2,3,3-tetrafluoropropene (HCFO-1214yb),        2,3-dichloro-1,1,3,3-tetrafluoropropene (HCFO-1214xc) and        3,3-dichloro-1,1,2,3-tetrafluoropropene (HCFO-1214yc);    -   chloropentafluoropropene (HCFO-1215), namely, in particular        1-chloropentafluoropropene, 2-chloropentafluoropropene and        3-chloropentafluoropropene;    -   hexafluoropropene (HFO-1216);    -   dichlorotrifluoropropene (HCFO-1223), namely, in particular        1,1-dichloro-3,3,3-trifluoropropene (HCFO-1223za),        1,2-dichloro-3,3,3-trifluoropropene (HCFO-1223xd),        2,3-dichloro-1,3,3-trifluoropropene (HCFO-1223xe),        1,3-dichloro-2,3,3-trifluoropropene (HCFO-1223yd),        1,2-dichloro-1,3,3-trifluoropropene (HCFO-1223xb),        2,3-dichloro-1,1,3-trifluoropropene (HCFO-1223xc),        1,1-dichloro-2,3,3-trifluoropropene (HCFO-1223ya),        1,3-dichloro-1,2,3-trifluoropropene (HCFO-1223yb),        3,3-dichloro-1,1,2-trifluoropropene (HCFO-1223yc),        3,3-dichloro-1,2,3-trifluoropropene (HCFO-1223ye),        1,3-dichloro-1,3,3-trifluoropropene (HCFO-1223zb) and        3,3-dichloro-1,1,3-trifluoropropene (HCFO-1223zc);    -   chlorotetrafluoropropene (HCFO-1224), namely, in particular        1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd),        1-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224zb),        2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe),        3-chloro-1,2,3,3-tetrafluoropropene (HCFO-1224ye),        3-chloro-1,1,3,3-tetrafluoropropene (HCFO-1224zc),        2-chloro-1,1,3,3-tetrafluoropropene (HCFO-1224xc),        1-chloro-1,2,3,3-tetrafluoropropene (HCFO-1224yb) and        3-chloro-1,1,2,3-tetrafluoropropene (HCFO-1224yc);    -   pentafluoropropene, namely, in particular        1,1,1,2,3-pentafluoropropene in trans form (HFO-1225yeE),        1,1,1,2,3-pentafluoropropene in cis form (HFO-1225yeZ),        1,1,3,3,3-pentafluoropropene (HFO-1225zc) and        1,1,2,3,3-pentafluoropropene (HFO-1225yc);    -   trichlorofluoropropene (HCFO-1231), namely, in particular        1,1,2-trichloro-3-fluoropropene (HCFO-1231xa),        1,2,3-trichloro-1-fluoropropene (HCFO-1231xb),        1,2,3-trichloro-3-fluoropropene (HCFO-1231xd),        2,3,3-trichloro-1-fluoropropene (HCFO-1231xe),        2,3,3-trichloro-3-fluoropropene (HCFO-1231xf),        1,1,3-trichloro-2-fluoropropene (HCFO-1231ya),        1,3,3-trichloro-2-fluoropropene (HCFO-1231yd),        3,3,3-trichloro-2-fluoropropene (HCFO-1231yf),        1,1,3-trichloro-3-fluoropropene (HCFO-1231za),        1,3,3-trichloro-1-fluoropropene (HFCO-1231zb),        1,3,3-trichloro-3-fluoropropene (HCFO-1231zd)        and3,3,3-trichloro-1-fluoropropene (HCFO-1231ze);    -   dichlorodifluoropropene (HCFO-1232), namely, in particular        2,3-dichloro-3,3-difluoropropene (HCFO-1232xf),        1,2-dichloro-1,3-difluoropropene (HCFO-1232xb),        2,3-dichloro-1,1-difluoropropene (HCFO-1232xc),        1,2-dichloro-3,3-difluoropropene (HCFO-1232xd),        2,3-dichloro-1,3-difluoropropene (HCFO-1232xe),        1,1-dichloro-2,3-difluoropropene (HCFO-1232ya),        1,3-dichloro-1,2-difluoropropene (HCFO-1232yb),        1,3-dichloro-2,3-difluoropropene (HCFO-1232yd),        3,3-dichloro-1,2-difluoropropene (HCFO-1232ye),        3,3-dichloro-2,3-difluoropropene (HCFO-1232yf),        1,1-dichloro-3,3-difluoropropene (HCFO-1232za),        1,3-dichloro-1,3-difluoropropene (HCFO-1232zb),        3,3-dichloro-1,1-difluoropropene (HCFO-1232zc),        1,3-dichloro-3,3-difluoropropene (HCFO-1232zd) and        3,3-dichloro-1,3-difluoropropene (HCFO-1232ze);    -   chlorotrifluoropropene, namely, in particular        2-chloro-1,1,3-trifluoropropene (HCFO-1233xc),        2-chloro-1,3,3-trifluoropropene (HCFO-1233xe),        1-chloro-1,2,3-trifluoropropene (HCFO-1233yb),        3-chloro-1,1,2-trifluoropropene (HCFO-1233yc),        1-chloro-2,3,3-trifluoropropene (HCFO-1233yd),        3-chloro-1,2,3-trifluoropropene (HCFO-1233ye),        3-chloro-2,3,3-trifluoropropene (HCFO-1233yf),        1-chloro-1,3,3-trifluoropropene (HCFO-1233zb),        3-chloro-1,1,3-trifluoropropene (HCFO-1233zc),        3-chloro-1,3,3-trifluoropropene (HCFO-1233ze),        2-chloro-3,3,3-trifluoro-propene (HCFO-1233xf) and        1-chloro-3,3,3-trifluoropropene in trans form (HCFO-1233zdE);    -   tetrafluoropropene, namely, in particular        1,1,2,3-tetrafluoropropene (HFO-1234yc),        2,3,3,3-tetrafluoropropene (HFO-1234yf),        1,2,3,3-tetrafluoropropene (HFO-1234ye),        1,1,3,3-tetrafluoropropene (HFO-1234zc),        1,3,3,3-tetrafluoropropene in cis form (HFO-1234zeZ) and        1,3,3,3-tetrafluoropropene in trans form (HFO-1234zeE);    -   chlorodifluoropropene (HCFO-1242), namely, in particular        3-chloro-3,3-difluoropropene (HCFO-1242zf),        3-chloro-1,3-difluoropropene (HCFO-1242ze),        2-chloro-1,1-difluoropropene (HCFO-1242xc),        2-chloro-1,3-difluoropropene (HCFO-1242xe),        2-chloro-3,3-difluoropropene (HCFO-1242xf),        1-chloro-1,2-difluoropropene (HCFO-1242yb),        1-chloro-2,3-difluoropropene (HCFO-1242yd),        3-chloro-1,2-difluoropropene (HCFO-1242ye),        3-chloro-2,3-difluoropropene (HCFO-1242yf),        1-chloro-1,3-difluoropropene (HCFO-1242zb),        3-chloro-1,1-difluoropropene (HCFO-1242zc) and        1-chloro-3,3-difluoropropene (HCFO-1242zd);    -   trifluoropropene, namely, in particular 1,1,2-trifluoropropene        (HFO-1243yc), 1,2,3-trifluoropropene (HFO-1243ye),        2,3,3-trifluoropropene (HFO-1243yf), 1,1,3-trifluoropropene        (HFO-1243zc), 1,3,3-trifluoropropene (HFO-1243ze) and        3,3,3-trifluoropropene (HFO-1243zf);    -   chlorofluoropropene (HCFO-1251), namely, in particular        1-chloro-3-fluoropropene (HCFO-1251zd), 1-chloro-1-fluoropropene        (HCFO-1251zb), 1-chloro-2-fluoropropene (HCFO-1251yd),        2-chloro-1-fluoropropene (HCFO-1251xe), 2-chloro-3-fluoropropene        (HCFO-1251yf), 3-chloro-2-fluoropropene (HCFO-1251xf),        3-chloro-1-fluoropropene (HCFO-1251ze and        3-chloro-3-fluoropropene (HCFO-1251zf);    -   difluoropropene (HFO-1252), namely, in particular        1,2-difluoropropene (HCFO-1252ye), 2,3-difluoropropene        (HCFO-1252yf), 1,1-difluoropropene (HCFO-1252zc),        1,3-difluoropropene (HCFO-1252ze) and 3,3-difluoropropene        (HCFO-1252zf); and    -   trifluoropropyne.

The compositions according to the invention may be ternary mixtures,i.e. mixtures of three compounds and only three.

The compositions according to the invention may be quaternary mixtures,i.e. mixtures of four compounds and only four.

The compositions according to the invention may be quinternary mixtures,i.e. mixtures of five compounds and only five.

The compositions according to the invention may be senary mixtures, i.e.mixtures of six compounds and only six.

The compositions according to the invention may also be mixtures ofseven compounds and only seven.

The compositions according to the invention may also be mixtures ofeight compounds and only eight.

The compositions according to the invention may also be mixturescomprising more than eight compounds.

According to one embodiment, the compositions according to the inventionconsist essentially of a mixture of HF, HCFO-1233zdZ and one or more(hydro)halocarbon compounds comprising from 1 to 3 carbon atoms—themaximum amount of impurities, other than these compounds, being, forexample, 2%, or 1%, or 0.5%, or 0.2%, or 0.1%, or 0.05%, or 0.02%, or0.01%.

According to one embodiment, the compositions of the invention consistof a mixture of HF, HCFO-1233zdZ and one or more (hydro)halocarboncompounds comprising from 1 to 3 carbon atoms.

According to one embodiment, the abovementioned (hydro)halocarboncompound(s) used in the compositions according to the invention arechosen from tetrachlorofluoropropanes, trichlorodifluoropropanes,dichlorotrifluoropropanes, chlorotetrafluoropropanes,pentafluoropropanes, dichlorodifluoropropenes, trichlorofluoropropenes,chlorotrifluoropropenes and tetrafluoropropenes, and mixtures thereof.

According to one embodiment, the abovementioned (hydro)halocarboncompound(s) used in the compositions according to the invention arechosen from HCFC-241fa, HCFC-242fa, HCFC-243fa, HCFC-244fa, HFC-245fa,HCFO-1232za, HCFO-1232zd, HCFO-1233zdE, HFO-1234zeZ and HFO-1234zeE.

According to one embodiment, the abovementioned (hydro)halocarboncompound(s) used in the compositions according to the invention arechosen from HFC-245fa, HCFO-1233zdE, HFO-1234zeZ and HFO-1234zeE.

According to one embodiment, the compositions according to the inventionmay consist (or consist essentially) of a mixture of HF, HCFO-1233zdEand HCFO-1233zdZ. The HF content in these compositions is advantageouslyfrom 1% to 85% and more preferentially from 5% to 80%. The boiling pointis preferably from 0 to 40° C. for a pressure from 0.6 to 4.0 barabsolute.

Alternatively, the compositions according to the invention may comprisea mixture of HF, HCFO-1233zdE, HCFO-1233zdZ and of one or more other(hydro)halocarbon compounds, which may be chosen from all the compoundslisted above; and which may be chosen especially from propanes andpropenes, which are partially or totally substituted with halogens; andwhich may be chosen especially from tetrachlorofluoropropanes,trichlorodifluoropropanes, dichlorotrifluoropropanes,chlorotetrafluoropropanes, pentafluoropropanes,dichlorodifluoropropenes, trichlorofluoropropenes,chlorotrifluoropropenes and tetrafluoropropenes; and which may be chosenespecially from HCFC-241fa, HCFC-242fa, HCFC-243fa, HCFC-244fa,HFC-245fa, HCFO-1232za, HCFO-1232zd, HFO-1234zeZ and HFO-1234zeE; andwhich may be chosen more particularly from HFC-245fa, HFO-1234zeZ andHFO-1234zeE.

According to one embodiment, the compositions according to the inventionmay consist (or consist essentially) of a mixture of HF, HCFO-1233zdE,HCFO-1233zdZ and HFC-245fa. The HF content in these compositions isadvantageously from 1% to 85% and more preferentially from 5% to 80%.The boiling point is preferably from 0 to 40° C. for a pressure from 0.6to 4.4 bar absolute.

Alternatively, the compositions according to the invention may comprisea mixture of HF, HCFO-1233zdE, HCFO-1233zdZ, HFC-245fa and of one ormore other (hydro)halocarbon compounds, which may be chosen from all thecompounds listed above; and which may be chosen especially from propanesand propenes, which are partially or totally substituted with halogens;and which may be chosen especially from tetrachlorofluoropropanes,trichlorodifluoropropanes, dichlorotrifluoropropanes,chlorotetrafluoropropanes, pentafluoropropanes,dichlorodifluoropropenes, trichlorofluoropropenes,chlorotrifluoropropenes and tetrafluoropropenes; and which may be chosenespecially from HCFC-241fa, HCFC-242fa, HCFC-243fa, HCFC-244fa,HCFO-1232za, HCFO-1232zd, HFO-1234zeZ and HFO-1234zeE; and which may bechosen more particularly from HFO-1234zeZ and HFO-1234zeE.

According to one embodiment, the compositions according to the inventionmay consist (or consist essentially) of a mixture of HF, HCFO-1233zdZ,HFO-1234zeZ and HFC-245fa. The HF content in these compositions isadvantageously from 1% to 85% and more preferentially from 5% to 80%.The boiling point is preferably from 0 to 40° C. for a pressure from 0.6to 4.8 bar absolute.

Alternatively, the compositions according to the invention may comprisea mixture of HF, HCFO-1233zdZ, HFO-1234zeZ, HFC-245fa and of one or moreother (hydro)halocarbon compounds, which may be chosen from all thecompounds listed above; and which may be chosen especially from propanesand propenes, which are partially or totally substituted with halogens;and which may be chosen especially from tetrachlorofluoropropanes,trichlorodifluoropropanes, dichlorotrifluoropropanes,chlorotetrafluoropropanes, pentafluoropropanes,dichlorodifluoropropenes, trichlorofluoropropenes,chlorotrifluoropropenes and tetrafluoropropenes; and which may be chosenespecially from HCFC-241fa, HCFC-242fa, HCFC-243fa, HCFC-244fa,HCFO-1232za, HCFO-1232zd, HCFO-1233zdE and HFO-1234zeE; and which may bechosen more particularly from HCFO-1233zdE and HFO-1234zeE.

According to one embodiment, the compositions according to the inventionmay consist (or consist essentially) of a mixture of HF, HCFO-1233zdZ,HFO-1234zeE and HFC-245fa. The HF content in these compositions isadvantageously from 1% to 80% and more preferentially from 5% to 75%.The boiling point is preferably from 0 to 40° C. for a pressure from 0.6to 8.6 bar absolute.

Alternatively, the compositions according to the invention may comprisea mixture of HF, HCFO-1233zdZ, HFO-1234zeE, HFC-245fa and of one or moreother (hydro)halocarbon compounds, which may be chosen from all thecompounds listed above; and which may be chosen especially from propanesand propenes, which are partially or totally substituted with halogens;and which may be chosen especially from tetrachlorofluoropropanes,trichlorodifluoropropanes, dichlorotrifluoropropanes,chlorotetrafluoropropanes, pentafluoropropanes,dichlorodifluoropropenes, trichlorofluoropropenes,chlorotrifluoropropenes and tetrafluoropropenes; and which may be chosenespecially from HCFC-241fa, HCFC-242fa, HCFC-243fa, HCFC-244fa,HCFO-1232za, HCFO-1232zd, HCFO-1233zdE and HFO-1234zeZ; and which may bechosen more particularly from HCFO-1233zdE and HFO-1234zeZ.

According to one embodiment, the compositions according to the inventionmay consist (or consist essentially) of a mixture of HF, HCFO-1233zdZ,HFO-1234zeE, HFO-1234zeZ and HFC-245fa. The HF content in thesecompositions is advantageously from 1% to 85% and more preferentiallyfrom 5% to 80%. The boiling point is preferably from 0 to 40° C. for apressure from 0.6 to 8.9 bar absolute.

Alternatively, the compositions according to the invention may comprisea mixture of HF, HCFO-1233zdZ, HFO-1234zeE, HFO-1234zeZ, HFC-245fa andof one or more other (hydro)halocarbon compounds, which may be chosenfrom all the compounds listed above;

and which may be chosen especially from propanes and propenes, which arepartially or totally substituted with halogens; and which may be chosenespecially from tetrachlorofluoropropanes, trichlorodifluoropropanes,dichlorotrifluoropropanes, chlorotetrafluoropropanes,pentafluoropropanes, dichlorodifluoropropenes, trichlorofluoropropenes,chlorotrifluoropropenes and tetrafluoropropenes; and which may be chosenespecially from HCFC-241fa, HCFC-242fa, HCFC-243fa, HCFC-244fa,HCFO-1232za, HCFO-1232zd and HCFO-1233zdE; and which may especially beHCFO-1233zdE.

According to one embodiment, the compositions according to the inventionmay consist (or consist essentially) of a mixture of HF, HCFO-1233zdZ,HCFO-1233zdE, HFO-1234zeE and HFC-245fa. The HF content in thesecompositions is advantageously from 1% to 85% and more preferentiallyfrom 5% to 80%. The boiling point is preferably from 0 to 40° C. for apressure from 0.6 to 8.9 bar absolute.

Alternatively, the compositions according to the invention may comprisea mixture of HF, HCFO-1233zdZ, HCFO-1233zdE, HFO-1234zeE, HFC-245fa andof one or more other (hydro)halocarbon compounds, which may be chosenfrom all the compounds listed above; and which may be chosen especiallyfrom propanes and propenes, which are partially or totally substitutedwith halogens; and which may be chosen especially fromtetrachlorofluoropropanes, trichlorodifluoropropanes,dichlorotrifluoropropanes, chlorotetrafluoropropanes,pentafluoropropanes, dichlorodifluoropropenes, trichlorofluoropropenes,chlorotrifluoropropenes and tetrafluoropropenes; and which may be chosenespecially from HCFC-241fa, HCFC-242fa, HCFC-243fa, HCFC-244fa,HCFO-1232za, HCFO-1232zd and HFO-1234zeZ; and which may especially beHFO-1234zeZ.

According to one embodiment, the compositions according to the inventionmay consist (or consist essentially) of a mixture of HF, HCFO-1233zdZ,HCFO-1233zdE, HFO-1234zeZ and HFC-245fa. The HF content in thesecompositions is advantageously from 1% to 85% and more preferentiallyfrom 5% to 80%. The boiling point is preferably from 0 to 40° C. for apressure from 0.6 to 4.8 bar absolute.

Alternatively, the compositions according to the invention may comprisea mixture of HF, HCFO-1233zdZ, HCFO-1233zdE, HFO-1234zeZ, HFC-245fa andof one or more other (hydro)halocarbon compounds, which may be chosenfrom all the compounds listed above; and which may be chosen especiallyfrom propanes and propenes, which are partially or totally substitutedwith halogens; and which may be chosen especially fromtetrachlorofluoropropanes, trichlorodifluoropropanes,dichlorotrifluoropropanes, chlorotetrafluoropropanes,pentafluoropropanes, dichlorodifluoropropenes, trichlorofluoropropenes,chlorotrifluoropropenes and tetrafluoropropenes; and which may be chosenespecially from HCFC-241fa, HCFC-242fa, HCFC-243fa, HCFC-244fa,HCFO-1232za, HCFO-1232zd and HFO-1234zeE; and which may especially beHFO-1234zeE.

According to one embodiment, the compositions according to the inventionmay consist (or consist essentially) of a mixture of HF, HCFO-1233zdZ,HCFO-1233zdE, HFO-1234zeE, HFO-1234zeZ and HFC-245fa. The HF content inthese compositions is advantageously from 1% to 85% and morepreferentially from 5% to 80%. The boiling point is preferably from 0 to40° C. for a pressure from 0.6 to 8.8 bar absolute.

Alternatively, the compositions according to the invention may comprisea mixture of HF, HCFO-1233zdZ, HCFO-1233zdE, HFO-1234zeE, HFO-1234zeZ,HFC-245fa and of one or more other (hydro)halocarbon compounds, whichmay be chosen from all the compounds listed above; and which may bechosen especially from propanes and propenes, which are partially ortotally substituted with halogens; and which may be chosen especiallyfrom tetrachlorofluoropropanes, trichlorodifluoropropanes,dichlorotrifluoropropanes, chlorotetrafluoropropanes,pentafluoropropanes, dichlorodifluoropropenes, trichlorofluoropropenes,chlorotrifluoropropenes and tetrafluoropropenes; and which may be chosenespecially from HCFC 241fa, HCFC-242fa, HCFC-243fa, HCFC-244fa, HFO1232za and HCFO-1232zd.

In general, in the compositions according to the invention, theproportion of HF is preferably from 1% to 85%, especially from 5% to 80%(relative to the total weight of the composition), more particularlyfrom 10% to 65%; and the proportion of (hydro)halocarbon compounds,including HCFO-1233zdZ, is from 15% to 99%, especially from 20% to 95%,more particularly from 35% to 90%.

The boiling point of a composition according to the invention ispreferably from −20° C. to 80° C. for a pressure from 0.1 to 44 barabsolute; advantageously from 0 to 40° C. for a pressure from 0.5 to 9bar absolute.

When the compositions according to the invention comprise bothHCFO-1233zdZ and HCFO-1233zdE, they may comprise, in mass proportionsrelative to the sum of these two compounds:

-   -   from 1% to 10% of HCFO-1233zdZ and from 90% to 99% of        HCFO-1233zdE;    -   from 10% to 20% of HCFO-1233zdZ and from 80% to 90% of        HCFO-1233zdE;    -   from 20% to 30% of HCFO-1233zdZ and from 70% to 80% of        HCFO-1233zdE;    -   from 30% to 40% of HCFO-1233zdZ and from 60% to 70% of        HCFO-1233zdE;    -   from 40% to 50% of HCFO-1233zdZ and from 50% to 60% of        HCFO-1233zdE;    -   from 50% to 60% of HCFO-1233zdZ and from 40% to 50% of        HCFO-1233zdE;    -   from 60% to 70% of HCFO-1233zdZ and from 30% to 40% of        HCFO-1233zdE;    -   from 70% to 80% of HCFO-1233zdZ and from 20% to 30% of        HCFO-1233zdE;    -   from 80% to 90% of HCFO-1233zdZ and from 10% to 20% of        HCFO-1233zdE;    -   from 90% to 99% of HCFO-1233zdZ and from 1% to 10% of        HCFO-1233zdE.

According to one embodiment, the compositions according to theinvention, in condensed form, comprise two liquid phases, one preferablybeing richer in HF than the other.

The invention may in particular be exploited in the context of processesfor producing a fluoro compound, in which mixtures of the compoundsdescribed above may be produced.

Such mixtures may then be treated by distillation so as to collect,firstly, a composition according to the invention, and, secondly, HF, oralternatively, thirdly, HCFO-1233zdZ, or alternatively, fourthly, one ormore other (hydro)halocarbon compounds.

Such mixtures may especially be obtained as a stream of products derivedfrom a reaction for the catalytic fluorination of a chloro compound to afluoro compound with HF.

The term “chloro compound” (which represents the main reagent of thecatalytic fluorination reaction) means an organic compound comprisingone or more chlorine atoms, and the term “fluoro compound” (whichrepresents the desired product of the catalytic fluorination reaction)means an organic compound comprising one or more fluorine atoms.

It is understood that the chloro compound may comprise one or morefluorine atoms, and that the fluoro compound may comprise one or morechlorine atoms. In general, the number of chlorine atoms in the fluorocompound is less than the number of chlorine atoms in the chlorocompound; and the number of fluorine atoms in the fluoro compound isgreater than the number of fluorine atoms in the chloro compound.

The chloro compound may be an alkane or an alkene optionally bearingsubstituents chosen from F, Cl, I and Br (preferably from F and Cl), andcomprising at least one Cl substituent.

The fluoro compound may be an alkane or an alkene optionally bearingsubstituents chosen from F, Cl, I and Br (preferably from F and Cl), andcomprising at least one F substituent.

The chloro compound may especially be an alkane with one or morechlorine substituents (hydrochlorocarbon or chlorocarbon) or an alkanewith one or more chlorine and fluorine substituents(hydrochlorofluorocarbon or chlorofluorocarbon) or an alkene with one ormore chlorine substituents (chloroolefin or hydrochloroolefin) or analkene with one or more chlorine and fluorine substituents(hydrochlorofluoroolefin or chlorofluoroolefin).

The fluoro compound may especially be an alkane with one or morefluorine substituents (fluorocarbon or hydrofluorocarbon) or an alkanewith one or more chlorine and fluorine substituents(hydrochlorofluorocarbon or chlorofluorocarbon) or an alkene with one ormore fluorine substituents (fluoroolefin or hydrofluoroolefin) or analkene with one or more chlorine and fluorine substituents(hydrochlorofluoroolefin or chlorofluoroolefin).

According to one embodiment, the chloro compound and the fluoro compoundcomprise only one carbon atom.

According to one embodiment, the chloro compound and the fluoro compoundcomprise two carbon atoms.

According to a particularly preferred embodiment, the chloro compoundand the fluoro compound comprise three carbon atoms.

The invention is especially found to apply to the following fluorinationreactions:

-   -   fluorination of 1,1,1,3,3-pentachloropropane to HCFO-1233zdE;    -   fluorination of 1,1,3,3-tetrachloropropene to HCFO-1233zdE.

The invention may especially apply to the determination of thedecantation and purification steps necessary for treating a gas streamexiting a liquid-phase fluorination reactor using1,1,3,3-tetrachloropropene as starting material or a gas-phasefluorination reactor using 1,1,1,3,3-pentachloropropane as startingmaterial. This gas stream may contain between 15% and 50% of HF, between15% and 50% of HCl and the remainder is constituted of all of theorganic compounds derived from the reaction.

In one embodiment, a liquid-phase fluorination process is performedusing 1,1,3,3-tetrachloropropene as starting material, and thedistribution of the organic compounds on conclusion of the reaction mayespecially be the following: from 85% to 95% of HCFO-1233zdE, from 0 to5% of HCFO-1233zdZ, from 0 to 3% of HFO-1234zeE, from 0 to 3% ofHFO-1234zeZ, from 0 to 3% of HFC-245fa, from 0 to 3% of HCFO-1232, from0 to 1% of HCFC-243 and from 0 to 1% of HCFC-241.

In one embodiment, a gas-phase fluorination process is performed using1,1,1,3,3-pentachloropropane as starting material, and the distributionof the organic compounds on conclusion of the reaction may especially bethe following: from 65% to 85% of HCFO-1233zdE, from 15% to 25% ofHCFO-1233zdZ, from 0 to 10% of HCFO-1232, from 0 to 3% of HFO-1234zeE,from 0 to 3% of HFO-1234zeZ, from 0 to 3% of HFC-245fa, from 0 to 3% ofHCFC-243.

The compositions according to the invention have advantageousproperties, in particular for the recycling of HF into the reactionstep. Thus, the condensed phase of these compositions, optionally whenthey are subjected to a distillation step and/or a liquid/liquidseparation step, such as by decantation, forms two immiscible liquidphases. The phase that is richer in HF may be recycled into the reactionstep, whereas the phase that is less rich in HF may be subjected to oneor more distillation steps to separate the organic compounds and toallow, for example, recycling into the reaction step of organiccompounds that are reaction intermediates.

EXAMPLES

The examples that follow illustrate the invention without limiting it.

Example 1 HF/HCFO-1233zdE/HCFO-1233zdZ Ternary Composition

Azeotropic and hetero-azeotropic behavior was observed for theHF/HCFO-1233zdE/HCFO-1233zdZ ternary mixture.

FIG. 1 illustrates the azeotropic behavior for the isotherm at 25° C.,for various HCFO-1233zdE/HCFO-1233zdZ proportions, namely:

-   -   A: 95% HCFO-1233zdE and 5% HCFO-1233zdZ (relative to the total        for the two);    -   B: 50% HCFO-1233zdE and 50% HCFO-1233zdZ (relative to the total        for the two);    -   C: 5% HCFO-1233zdE and 95% HCFO-1233zdZ (relative to the total        for the two).

It is found that the composition has a boiling point of 0 to 40° C. fora pressure from 0.6 bar absolute to 4.0 bar absolute approximately.Thus, for a mixture of HF with 50% HCFO-1233zdZ and 50% HCFO-1233zdE(the proportions being relative to the sum for the two), the boilingpoint is 0° C. at about 0.9 bar absolute, 25° C. at about 2.1 barabsolute and 40° C. at about 3.5 bar absolute.

The decantation ranges for a mixture of HF with 50% HCFO-1233zdZ and 50%HCFO-1233zdE (the proportions being relative to the sum for the two)are: from 5% to 75% HF at 0° C.; from 5% to 70% HF at 25° C.; and from5% to 60% HF at 40° C.

Example 2 HF/HCFO-1233zdZ/HFO-1234zeE/HFC-245fa Quaternary Composition

Azeotropic and hetero-azeotropic behavior was observed for theHF/HCFO-1233zdZ/HFO-1234zeE/HFC-245fa quaternary mixture.

FIG. 2 illustrates the azeotropic behavior for the isotherm at 25° C.,for various HCFO-1233zdZ/HFO-1234zeE/HFC-245fa proportions, namely:

-   -   A: 5% HCFO-1233zdZ, 90% HFO-1234zeE and 5% HFC-245fa (relative        to the total for the three);    -   B: 40% HCFO-1233zdZ, 30% HFO-1234zeE and 30% HFC-245fa (relative        to the total for the three);    -   C: 5% HCFO-1233zdZ, 5% HFO-1234zeE and 90% HFC-245fa (relative        to the total for the three);    -   D: 90% HCFO-1233zdZ, 5% HFO-1234zeE and 5% HFC-245fa (relative        to the total for the three).

It is found that the composition has a boiling point of 0 to 40° C. fora pressure from 0.6 bar absolute to 8.6 bar absolute approximately.

The decantation ranges for a mixture comprising equal mass proportionsof HCFO-1233zdZ, HFO-1234zeE and HFC-245fa are: from 5% to 80% HF at 0°C.; from 5% to 75% HF at 25° C.; and from 5% to 70% HF at 40° C.

Example 3 HF/HCFO-1233zdZ/HFO-1234zeZ/HFC-245fa Quaternary Composition

Azeotropic and hetero-azeotropic behavior was observed for theHF/HCFO-1233zdZ/HFO-1234zeZ/HFC-245fa quaternary mixture.

FIG. 3 illustrates the azeotropic behavior for the isotherm at 25° C.,for various HCFO-1233zdZ/HFO-1234zeZ/HFC-245fa proportions, namely:

-   -   A: 5% HCFO-1233zdZ, 90% HFO-1234zeZ and 5% HFC-245fa (relative        to the total for the three);    -   B: 5% HCFO-1233zdZ, 5% HFO-1234zeZ and 90% HFC-245fa (relative        to the total for the three);    -   C: 40% HCFO-1233zdZ, 30% HFO-1234zeZ and 30% HFC-245fa (relative        to the total for the three);    -   D: 90% HCFO-1233zdZ, 5% HFO-1234zeZ and 5% HFC-245fa (relative        to the total for the three).

It is found that the composition has a boiling point of 0 to 40° C. fora pressure from 0.6 bar absolute to 4.8 bar absolute approximately.

The decantation ranges for a mixture comprising equal mass proportionsof HCFO-1233zdZ, HFO-1234zeZ and HFC-245fa are: from 5% to 80% HF at 0°C.; from 5% to 75% HF at 25° C.; and from 5% to 75% HF at 40° C.

Example 4 HF/HCFO-1233zdE/HCFO-1233zdZ/HFC-245fa Quaternary Composition

Azeotropic and hetero-azeotropic behavior was observed for theHF/HCFO-1233zdE/HCFO-1233zdZ/HFC-245fa quaternary mixture.

FIG. 4 illustrates the azeotropic behavior for the isotherm at 25° C.,for various HCFO-1233zdE/HCFO-1233zdZ/HFC-245fa proportions, namely:

-   -   A: 5% HCFO-1233zdE, 5% HCFO-1233zdZ and 90% HFC-245fa (relative        to the total for the three);    -   B: 90% HCFO-1233zdE, 5% HCFO-1233zdZ and 5% HFC-245fa (relative        to the total for the three);    -   C: 40% HCFO-1233zdE, 30% HCFO-1233zdZ and 30% HFC-245fa        (relative to the total for the three);    -   D: 5% HCFO-1233zdE, 90% HCFO-1233zdZ and 5% HFC-245fa (relative        to the total for the three).

It is found that the composition has a boiling point of 0 to 40° C. fora pressure from 0.6 bar absolute to 4.4 bar absolute approximately.

The decantation ranges for a mixture comprising equal mass proportionsof HCFO-1233zdE, HCFO-1233zdZ and HFC-245fa are: from 5% to 80% HF at 0°C.; from 5% to 75% HF at 25° C.; and from 5% to 75% HF at 40° C.

Example 5 HF/HCFO-1233zdZ/HFO-1234zeE/HFO-1234zeZ/HFC-245fa QuinternaryComposition

Azeotropic and hetero-azeotropic behavior was observed for theHF/HCFO-1233zdZ/HFO-1234zeE/HFO-1234zeZ/HFC-245fa quinternary mixture.

FIG. 5 illustrates the azeotropic behavior for the isotherm at 25° C.,for various HCFO-1233zdZ/HFO-1234zeE/HFO-1234zeZ/HFC-245fa proportions,namely:

-   -   A: 1% HCFO-1233zdZ, 97% HFO-1234zeE, 1% HFO-1234zeZ and 1%        HFC-245fa (relative to the total for the four);    -   B: 25% HCFO-1233zdZ, 25% HFO-1234zeE, 25% HFO-1234zeZ and 25%        HFC-245fa (relative to the total for the four);    -   C: 1% HCFO-1233zdZ, 1% HFO-1234zeE, 97% HFO-1234zeZ and 1%        HFC-245fa (relative to the total for the four);    -   D: 1% HCFO-1233zdZ, 1% HFO-1234zeE, 1% HFO-1234zeZ and 97%        HFC-245fa (relative to the total for the four);    -   E: 97% HCFO-1233zdZ, 1% HFO-1234zeE, 1% HFO-1234zeZ and 1%        HFC-245fa (relative to the total for the four).

It is found that the composition has a boiling point of 0 to 40° C. fora pressure from 0.6 bar absolute to 8.9 bar absolute approximately.

The decantation ranges for a mixture comprising equal mass proportionsof HCFO-1233zdZ, HFO-1234zeE, HFO-1234zeZ and HFC-245fa are: from 5% to80% HF at 0° C.; from 5% to 75% HF at 25° C.; and from 5% to 65% HF at40° C.

Example 6 HF/HCFO-1233zdE/HCFO-1233zdZ/HFO-1234zeE/HFC-245fa QuinternaryComposition

Azeotropic and hetero-azeotropic behavior was observed for theHF/HCFO-1233zdE/HCFO-1233zdZ/HFO-1234zeE/HFC-245fa quinternary mixture.

FIG. 6 illustrates the azeotropic behavior for the isotherm at 25° C.,for various HCFO-1233zdE/HCFO-1233zdZ/HFO-1234zeE/HFC-245fa proportions,namely:

-   -   A: 1% HCFO-1233zdE, 1% HCFO-1233zdZ, 97% HFO-1234zeE and 1%        HFC-245fa (relative to the total for the four);    -   B: 25% HCFO-1233zdE, 25% HCFO-1233zdZ, 25% HFO-1234zeE and 25%        HFC-245fa (relative to the total for the four);    -   C: 1% HCFO-1233zdE, 1% HCFO-1233zdZ, 1% HFO-1234zeE and 97%        HFC-245fa (relative to the total for the four);    -   D: 97% HCFO-1233zdE, 1% HCFO-1233zdZ, 1% HFO-1234zeE and 1%        HFC-245fa (relative to the total for the four);    -   E: 1% HCFO-1233zdE, 97% HCFO-1233zdZ, 1% HFO-1234zeE and 1%        HFC-245fa (relative to the total for the four).

It is found that the composition has a boiling point of 0 to 40° C. fora pressure from 0.6 bar absolute to 8.9 bar absolute approximately.

The decantation ranges for a mixture comprising equal mass proportionsof HCFO-1233zdE, HCFO-1233zdZ, HFO-1234zeE and HFC-245fa are: from 5% to80% HF at 0° C.; from 5% to 75% HF at 25° C.; and from 5% to 65% HF at40° C.

Example 7 HF/HCFO-1233zdE/HCFO-1233zdZ/HFO-1234zeZ/HFC-245fa QuinternaryComposition

Azeotropic and hetero-azeotropic behavior was observed for theHF/HCFO-1233zdE/HCFO-1233zdZ/HFO-1234zeZ/HFC-245fa quinternary mixture.

FIG. 7 illustrates the azeotropic behavior for the isotherm at 25° C.,for various HCFO-1233zdE/HCFO-1233zdZ/HFO-1234zeZ/HFC-245fa proportions,namely:

-   -   A: 1% HCFO-1233zdE, 1% HCFO-1233zdZ, 97% HFO-1234zeZ and 1%        HFC-245fa (relative to the total for the four);    -   B: 1% HCFO-1233zdE, 1% HCFO-1233zdZ, 1% HFO-1234zeZ and 97%        HFC-245fa (relative to the total for the four);    -   C: 25% HCFO-1233zdE, 25% HCFO-1233zdZ, 25% HFO-1234zeZ and 25%        HFC-245fa (relative to the total for the four);    -   D: 97% HCFO-1233zdE, 1% HCFO-1233zdZ, 1% HFO-1234zeZ and 1%        HFC-245fa (relative to the total for the four);    -   E: 1% HCFO-1233zdE, 97% HCFO-1233zdZ, 1% HFO-1234zeZ and 1%        HFC-245fa (relative to the total for the four).

It is found that the composition has a boiling point of 0 to 40° C. fora pressure from 0.6 bar absolute to 4.8 bar absolute approximately.

The decantation ranges for a mixture comprising equal mass proportionsof HCFO-1233zdE, HCFO-1233zdZ, HFO-1234zeZ and HFC-245fa are: from 5% to80% HF at 0° C.; from 5% to 75% HF at 25° C.; and from 5% to 70% HF at40° C.

Example 8 HF/HCFO-1233zdE/HCFO-1233zdZ/HFO-1234zeE/HFO-1234zeZ/HFC-245faSenary Composition

Azeotropic and hetero-azeotropic behavior was observed for theHF/HCFO-1233zdE/HCFO-1233zdZ/HFO-1234zeE/HFO-1234zeZ/HFC-245fa senarymixture.

FIG. 8 illustrates the azeotropic behavior for the isotherm at 25° C.,for various HCFO-1233zdE/HCFO-1233zdZ/HFO-1234zeE/HFO-1234zeZ/HFC-245faproportions, namely:

-   -   A: 1% HCFO-1233zdE, 1% HCFO-1233zdZ, 96% HFO-1234zeE, 1%        HFO-1234zeZ and 1% HFC-245fa (relative to the total for the        five);    -   B: 20% HCFO-1233zdE, 20% HCFO-1233zdZ, 20% HFO-1234zeE, 20%        HFO-1234zeZ and 20% HFC-245fa (relative to the total for the        five);    -   C: 1% HCFO-1233zdE, 1% HCFO-1233zdZ, 1% HFO-1234zeE, 96%        HFO-1234zeZ and 1% HFC-245fa (relative to the total for the        five);    -   D: 1% HCFO-1233zdE, 1% HCFO-1233zdZ, 1% HFO-1234zeE, 1%        HFO-1234zeZ and 96% HFC-245fa (relative to the total for the        five);    -   E: 96% HCFO-1233zdE, 1% HCFO-1233zdZ, 1% HFO-1234zeE, 1%        HFO-1234zeZ and 1% HFC-245fa (relative to the total for the        five);    -   F: 1% HCFO-1233zdE, 96% HCFO-1233zdZ, 1% HFO-1234zeE, 1%        HFO-1234zeZ and 1% HFC-245fa (relative to the total for the        five).

It is found that the composition has a boiling point of 0 to 40° C. fora pressure from 0.6 bar absolute to 8.8 bar absolute approximately.

The decantation ranges for a mixture comprising equal mass proportionsof HCFO-1233zdE, HCFO-1233zdZ, HFO-1234zeE, HFO-1234zeZ and HFC-245faare: from 5% to 80% HF at 0° C.; from 5% to 75% HF at 25° C.; and from5% to 65% HF at 40° C.

Embodiments

1. An azeotropic or quasi-azeotropic composition comprising hydrogenfluoride, Z-3,3,3-trifluoro-1-chloropropene and one or more(hydro)halocarbon compounds comprising from 1 to 3 carbon atoms.

2. The composition as in embodiment 1, in which the (hydro)halocarboncompound(s) comprise three carbon atoms, and are preferably chosen frompropanes and propenes that are partially or totally substituted withhalogens.

3. The composition as in embodiment 1 or 2, in which the(hydro)halocarbon compound(s) are chosen from tetrachlorofluoropropanes,trichlorodifluoropropanes, dichlorotrifluoropropanes,chlorotetrafluoropropanes, pentafluoropropanes,dichlorodifluoropropenes, trichlorofluoropropenes,chlorotrifluoropropenes and tetrafluoropropenes.

4. The composition as in one of embodiments 1 to 3, comprising hydrogenfluoride, Z-3,3,3-trifluoro-1-chloropropene,E-3,3,3-trifluoro-1-chloropropene and one or more other(hydro)halocarbon compounds comprising from 1 to 3 carbon atoms.

5. The composition as in one of embodiments 1 to 4, comprising hydrogenfluoride, Z-3,3,3-trifluoro-1-chloropropene,E-1,3,3,3-tetrafluoropropene and one or more other (hydro)halocarboncompounds comprising from 1 to 3 carbon atoms.

6. The composition as in one of embodiments 1 to 5, comprising hydrogenfluoride, Z-3,3,3-trifluoro-1-chloropropene,Z-1,3,3,3-tetrafluoropropene and one or more other (hydro)halocarboncompounds comprising from 1 to 3 carbon atoms.

7. The composition as in one of embodiments 1 to 6, comprising hydrogenfluoride, Z-3,3,3-trifluoro-1-chloropropene,1,1,1,3,3-pentafluoropropane and one or more other (hydro)halocarboncompounds comprising from 1 to 3 carbon atoms.

8. The composition as in one of embodiments 1 to 7, which is a ternarymixture, and is preferably a mixture of hydrogen fluoride,Z-3,3,3-trifluoro-1-chloropropene and E-3,3,3-trifluoro-1-chloropropene.

9. The composition as in one of embodiments 1 to 7, which is aquaternary mixture, and is preferably a mixture of:

-   -   hydrogen fluoride, Z-3,3,3-trifluoro-1-chloropropene,        E-3,3,3-trifluoro-1-chloropropene and        1,1,1,3,3-pentafluoropropane; or    -   hydrogen fluoride, Z-3,3,3-trifluoro-1-chloropropene,        E-1,3,3,3-tetrafluoropropene and 1,1,1,3,3-pentafluoropropane;        or    -   hydrogen fluoride, Z-3,3,3-trifluoro-1-chloropropene,        Z-1,3,3,3-tetrafluoropropene and 1,1,1,3,3-pentafluoropropane.

10. The composition as in one of embodiments 1 to 7, which is aquinternary mixture, and is preferably a mixture of:

-   -   hydrogen fluoride, Z-3,3,3-trifluoro-1-chloropropene,        E-3,3,3-trifluoro-1-chloropropene, Z-1,3,3,3-tetrafluoropropene        and 1,1,1,3,3-pentafluoropropane; or    -   hydrogen fluoride, Z-3,3,3-trifluoro-1-chloropropene,        E-3,3,3-trifluoro-1-chloropropene, E-1,3,3,3-tetrafluoropropene        and 1,1,1,3,3-pentafluoropropane; or    -   hydrogen fluoride, Z-3,3,3-trifluoro-1-chloropropene,        Z-1,3,3,3-tetrafluoropropene, E-1,3,3,3-tetrafluoropropene and        1,1,1,3,3-pentafluoropropane.

11. The composition as in one of embodiments 1 to 7, which is a senarymixture, and is preferably a mixture of:

-   -   hydrogen fluoride, Z-3,3,3-trifluoro-1-chloropropene,        E-3,3,3-trifluoro-1-chloropropene, Z-1,3,3,3-tetrafluoropropene,        E-1,3,3,3-tetrafluoropropene and 1,1,1,3,3-pentafluoropropane.

12. The composition as in one of embodiments 1 to 11, which ishetero-azeotropic or quasi-hetero-azeotropic.

13. The composition as in one of embodiments 1 to 12, which comprisesfrom 1% to 85% by weight, preferably from 1% to 80% by weight, moreparticularly preferably from 5% to 80% by weight and most particularlypreferably from 5% to 75% by weight of hydrogen fluoride; and/or from15% to 99% by weight, preferably from 20% to 99% by weight, moreparticularly preferably from 20% to 95% by weight and most particularlypreferably from 25% to 95% by weight of (hydro)halocarbon compoundscomprising from 1 to 3 carbon atoms.

14. The composition as in one of embodiments 1 to 13, which has aboiling point of 0 to 40° C. for a pressure from 0.5 to 9 bar absolute.

15. A process for producing a main (hydro)halocarbon compound,comprising:

-   -   the formation of a mixture of compounds comprising hydrogen        fluoride, Z-3,3,3-trifluoro-1-chloropropene and one or more        other (hydro)halocarbon compounds;    -   distillation of this mixture making it possible to collect,        firstly, an azeotropic composition as in one of embodiments 1 to        14, and, secondly, at least one of the compounds of the mixture.

16. The process as in embodiment 15, in which distillation makes itpossible to collect, firstly, an azeotropic composition as in one ofembodiments 1 to 14, and, secondly, hydrogen fluoride; or alternatively,firstly, an azeotropic composition as in one of embodiments 1 to 14,and, secondly, E-3,3,3-trifluoro-1-chloropropene.

17. The process as in embodiment 15 or 16, which is a process forproducing 3,3,3-trifluoro-1-chloropropene, and preferablyE-3,3,3-trifluoro-1-chloropropene.

18. The process as in one of embodiments 15 to 17, in which the mixtureof compounds is obtained after a fluorination step, comprising thereaction of a chloro compound with hydrogen fluoride.

19. The process as in one of embodiments 15 to 18, in which theazeotropic composition collected is separated, preferably bydecantation, into two immiscible liquid fractions, namely a fractionrich in hydrogen fluoride and a fraction poor in hydrogen fluoride, thefraction rich in hydrogen fluoride containing a higher proportion ofhydrogen fluoride than the fraction poor in hydrogen fluoride; and thefraction rich in hydrogen fluoride being, where appropriate, recycledinto the fluorination step.

20. The process as in one of embodiments 15 to 19, in which the chlorocompound is 1,1,1,3,3-pentachloropropane or 1,1,3,3-tetrachloropropene.

1. A process for producing a main (hydro)halocarbon compound, comprising: the formation of a mixture of compounds comprising hydrogen fluoride, Z-3,3,3-trifluoro-1-chloropropene and one or more other (hydro)halocarbon compounds comprising from 1 to 3 carbon atoms; distillation of the mixture making it possible to collect, firstly, an azeotropic composition comprising hydrogen fluoride, Z-3,3,3-trifluoro-1-chloropropene and one or more (hydro)halocarbon compounds comprising from 1 to 3 carbon atoms, and, secondly, at least one of the compounds of the mixture.
 2. The process as claimed in claim 1, in which distillation makes it possible to collect, firstly, the azeotropic composition, and, secondly, hydrogen fluoride.
 3. The process as claimed in claim 1, in which distillation makes it possible to collect, firstly, the azeotropic composition, and, secondly, E-3,3,3-trifluoro-1-chloropropene.
 4. The process as claimed in claim 1, which is a process for producing 3,3,3-trifluoro-1-chloropropene.
 5. The process as claimed in claim 1, which is a process for producing E-3,3,3-trifluoro-1-chloropropene.
 6. The process as claimed in claim 1, in which the mixture of compounds is obtained after a fluorination step, comprising the reaction of a chloro compound with hydrogen fluoride.
 7. The process as claimed in claim 6, in which the azeotropic composition collected is separated into two immiscible liquid fractions, namely a fraction rich in hydrogen fluoride and a fraction poor in hydrogen fluoride, the fraction rich in hydrogen fluoride containing a higher proportion of hydrogen fluoride than the fraction poor in hydrogen fluoride; and the fraction rich in hydrogen fluoride being, where appropriate, recycled into the fluorination step.
 8. The process as claimed in claim 7, in which the azeotropic composition collected is separated by decantation.
 9. The process as claimed in claim 6, in which the chloro compound is 1,1,1,3,3-pentachloropropane or 1,1,3,3-tetrachloropropene.
 10. The process as claimed in claim 1, in which the (hydro)halocarbon compound(s) comprise three carbon atoms, and are preferably chosen from propanes and propenes that are partially or totally substituted with halogens.
 11. The process as claimed in claim 1, in which the (hydro)halocarbon compound(s) are chosen from tetrachlorofluoropropanes, trichlorodifluoropropanes, dichlorotrifluoropropanes, chlorotetrafluoropropanes, pentafluoropropanes, dichlorodifluoropropenes, trichlorofluoropropenes, chlorotrifluoropropenes and tetrafluoropropenes. 